DRY FRACTIONATION

1. Historical perspective

In edible oil processing, a fractionation process consists of a controlled cooling of the oil, thereby inducing a

partial, or fractional, crystallization. The remaining liquid (olein) is then separated from the solid fraction

(stearin) by means of a filtration or centrifugation.

This kind of fractionation process has been applied for almost 150 years. In most literature, Hippolyte

Mge-Mouris is credited with the invention of a patented method to produce certain fats of animal origin.

In fact, he concocted the production of a sort of margarine fat, by separating a liquid fraction from ordinary

tallow after gentle cooling. But with only temperature difference as the driving force, a fractional

crystallization of a fat is a perfectly natural, spontaneous phenomenon. So it was also observed that in palm

(kernel) oil harvested in tropical regions, small crystals would appear upon cooling and form a crystal

suspension in the wooden barrels during shipping to chillier Western Europe. These slightly denser solids

eventually settled, and such fractions could effectively replace hardened fats in margarines [1]. In a more

evocative twist, we could therefore consider these wooden shipping drums the very first oil crystallizers, with

just the peaceful ocean waves providing the necessary agitation to keep the mix in suspension. Moreover,

the natural fractional crystallization of fats when mildly cooled is echoed in the term winterization, referring

to the habit of leaving large oil tanks quiescent in wintertime to induce some mild crystallization and obtain a

liquid fraction with improved cold stability, in an economic fashion [2].

Despite the apparent spontaneity of the process itself, it took until the years 1960 for the fractionation

industry (and technology) to boom, when the production of palm oil in South-East Asia heavily increased and
export taxes on processed palm oil were reduced. At that time however, the boundaries of the technology

were mainly determined by the phase separation. In the early stages of fractionation technology, the olein

and stearin fractions of oils and fats had to be separated by settling, using only the force of gravity to bring

about a separation between the heavier solid phase and the lighter liquid phase, which left the settled solid

phase containing large quantities of entrained (trapped) liquid oil, almost certainly more than 75% [3]. In the

last decades, the continuous development of separation techniques, from vacuum belt filtration to

centrifuges and membrane press filters, has put fractionation on the map as a versatile and economic

modification technique. Although some specific techniques relying on use of detergents are still applied for

very particular production, actually only two main fractionation technologies are used in the 21st centurys

edible oil industry:

o Dry fractionation, also known as crystallization from the melt, is fractional crystallization in its most

simple form, and the economy of the technology allows it to be used for production of commodity fats. Dry

fractionation has long been regarded as an unpredictable, tedious and labor-intensive process. However,

the relatively cheap dry fractionation technique has evolved to the modification technology of the 21st

century [4], as without additives, polluting effluents or post-refining involved, the sustainability and safety

of the process is second to none.

o Solvent fractionation, already patented in the 1950s, involves the use of hexane or acetone to let

the high-melting components crystallize in a very low-viscous organic solvent. This can be helpful with

respect to the selectivity of the reaction, but mainly offers advantages in the field of phase separation:

much purer solid fractions can be obtained, even with a vacuum filtration. Being a more expensive

process, it is less common than dry fractionation and only comes into the picture when a very high added

value of (at least one of) the resulting fractions makes up for the high cost.

In this contribution, the emphasis is on dry fractionation technology.

2. The Crystallization Stage

Principal concepts

A controlled crystallization of the melt is the backbone of any dry fractionation process, and the success of

this process relies principally on the phase behavior of the constituent triglyceridess. Therefore it is probably

useful to dedicate some words to that part of the physical chemistry of fats and oils that lies at the basis of

the fractionation technology.

If anything is clear from browsing through the Lipid Library, it is the fact that a natural oil is a very complex

mixture of different triglycerides (not to mention diglycerides, free fatty acids, phospholipids, sterols, and

uncountable other minor constituents). The mix of triglycerides does have a repercussion on the melting

behavior of a fat: it does not exhibit a sharp melting point, but often displays a steady softening (or

increasing liquid content) with increasing temperature, until it is completely liquid. The position and width of

this melting range on a temperature scale is determined by the type of constituting triglycerides and

compositional heterogeneity of the oil:

o The type of the triglycerides: in a very simple approach, the longer the fatty acid moieties, the larger

the total molecule and consequently, the more energy (i.e. higher temperature) will be required to convert

such triglycerides from a solid to a liquid state. A double bond in the carbon chain decreases the melting

point dramatically, however, and this is why oils containing a high proportion of unsaturated fatty acids are

generally liquid.
o The broader the spectrum of triglycerides present in the oil, the broader the melting range. Some of

the triglycerides will only solidify (or melt) at 5C, whereas others will still be hard as candle wax at room

temperature.

Another matter to take into consideration is the respective concentration of each of these triglycerides. This

makes two variables to consider if a certain triglyceride will remain in the melt or crystallize: the temperature

and its concentration (in fact, just the same principle applies for sugar in coffee). So, ideal solubility

calculations based on the melting temperature and enthalpy of the pure solute, as well as the absolute

temperature as the principal variables, can serve as first approach the solubility of a triglyceride in a solvent.

But this premise of ideality is the real issue in fractional crystallization of oil: these are not regular solutions,

the triglycerides are not dissolved in an inert solvent; they are dissolved in a melt, i.e. other triglycerides.

Thus, the fact that the solvent and solute have quite some structural similarity leads to considerable

deviations from the ideal solubility. The most relevant is the occurrence of intersolubility in a solid state: the

property to form a solid solution in which the constituting triglycerides cannot be separately determined, nor

divided: it behaves as one phase. Consequently, such intersolubility of the triglycerides often presents the

largest fundamental problem in several fractionation processes, as the actual goal of fractionation is to

separate different triglycerides selectively.

It is fair to state that other typical fat crystallization phenomena such as polymorphism are of secondary

importance compared to intersolubility; typical fractionation conditions are generally sufficiently restricted in

time and temperature range to only allow one type of molecular arrangement to form. For palm oil, this is

typically in a -form from start to finish.

Intersolubility is also increased at higher degrees of supercooling, so if the fractional crystallization is to

occur selectively, the challenge for the process engineer is to steer clear from such conditions and keep the

melt just deep enough in metastable conditions to create a driving force for crystallization of the triglycerides

of interest, but not too deep as to prevent formation of solid solutions or uncontrolled crystal growth. If the

crystal growth is well controlled, the crystal aggregates result in sharply discrete and dense spherulitic

structures, sometimes measuring up to several millimeters in diameter, which are fairly uniform in size and

shape (Figure 1).

 Figure 1. Polarized light microscopic picture of typical spherulitic crystals developing in palm oil fractions.

To be complete, the influence of minor components is not one to be captured in one phrase, but overall

impurities such as diglycerides have a negative effect on crystal growth and filterability of the formed solids.

Also product-wise, it should be kept in mind that dry fractionation is a rubbish in, rubbish out process, so a

feedstock with a lot of impurities will never result in two clean fractions.

Conducting fractional crystallization

The basic principles sketched in the former paragraphs help to explain the key aspects of a crystallizer, the

technological heart of the fractionation installation. It should be able to gently cool down a mass of oil (up to

100 ton/batch) and keep the resulting crystal suspension as homogeneous as possible. Note that such
gentle cooling means in fact imposing very low supercooling conditions, and it will result in a formation of

fewer and larger crystals, because the said conditions simply rule out the existence of a mass of tiny

crystals. Fat crystallization is a fairly exothermic reaction (up to 180 kJ can be released for every kg of

crystals formed), so the efficiency with which this energy can be removed is an important design feature. For

most industrial crystallizers, this ranges between 120 and 200 W/m2.K.

The problem with occurrence of excessive intersolubility at higher degrees of supercooling explains the very

need for a (in terms of temperature) homogenizing crystallizer. Too steep temperature gradients within the

crystallizer will lead to formation of viscous solid solutions near the cooling wall (the coldest spot), while oil

entrapped in dead zones or with insufficient heat exchange with a cooling wall could encounter too high

temperatures to crystallize at an acceptable rate. Note that two extreme temperatures will not result in an

average degree of crystallization, but in a viscous slurry of badly filterable solid solution-crystals in a matrix
of unstable, hazy liquid. At these unfortunate occasions, it is comforting to remember that a dry fractionation

process is 100% reversible, and that upon heating, this mess will revert to the melt again, ready for another

attempt...

In order to preserve the selectivity and to avoid the temperature gradients within the melt, the cooling rate

under crystallization conditions is quite slow (0.2-3C/h), depending on the sensitivity of the reaction and the

performance of the crystallizer. Sensitivity of the reaction might be a little of a subjective term, but it can be

quite elegantly illustrated by Figure 2. This shows a Differential Scanning Calorimetry profile of palm oil (full

line above) and palm olein (dotted line below).

Figure 2. DSC cooling profile (-5C/min) of palm oil and its derived palm olein fraction. Exothermal peaks

are shown upwards.

The upward peaks in the profile show at which temperatures and how much heat of crystallization will be

released upon cooling (here at 5C/min!). For palm oil, the sharp peak on the right is created by the fast

solidification of predominantly trisaturated triglycerides. It is largely (and not solely, as some intersolubility

will inevitably occur) this fraction that is crystallized in the first step or cut in multistage palm oil

fractionation. Although the absolute temperatures in this diagram are not really relevant for fractionation
because of the high cooling rate, the diagram suggests clearly how simple fractional crystallization can be:

you put the temperature in between the two peaks and wait for the solidification to take place. When this first

trisaturated fraction is removed, however, the remaining palm olein shows one large peak, and it is instantly

clear that a slow fractional crystallization of a distinct fraction is a lot harder to accomplish in this matrix:

there is a lot more material to crystallize in a narrow temperature region, and intersolubility will have its say.

The cooling medium removing this heat of crystallization from crystallizers is typically clean cooling tower

water, sometimes mixed with some propylene glycol to be able to work at subzero conditions (as in fish oil

fractionation). Cooling by ammonia evaporation can also be considered, but very often turns out to be too

expensive for a classic installation. The cooling wall itself can be double-jacket, stainless steel cooling fins

(plates) or pipes. Normally, a cooling surface of at least 4m 2 per m3 oil is expected to assure proper heat

transfer for bulk edible oil fractionation.

In programming the cooling regime, generally three temperature parameters can be kept in check: the

cooling medium temperature, the oil temperature or sometimes also T, the temperature difference between

oil and cooling medium. The subtlety of the process then exists in knowing which cooling rate and cooling

modus to apply at which exact stage in the process, for there is no art in crash-cooling the lot. This is where

the process technologist can make a true impact on the outcome of the process, as a difference in cooling

regime could lead to a different process cycle time, filterability of the slurry and overall economy of the

process.

For a given cooling rate and heat exchange surface, the appropriate removal of released crystallization heat

to the cooling medium is also function of the agitation and the viscosity of the bulk. The first being an

externally imposed process feature, the type and intensity of agitation is indeed a typical design matter and

linked with the concept of the crystallizer. It should be sufficient to enhance heat transfer and favor crystal

initiation and secondary crystallization, but on the other hand excessive agitation could damage the

structures of the crystals being formed, which might present problems in the subsequent filtration stage.

Viscosity on the other hand, is an intrinsic state of the oil (though to be fully correct, an edible oil crystal

suspension does exhibit some shear-thinning behavior). Excessive viscosities will reduce mass and heat

transfer between solid and liquid, hence decreasing the crystal growth rate, also by limiting molecular

diffusion. The flow properties of the oil are not only a function of solids concentration present in the liquid,

but are also greatly influenced by the interactions between the different crystal entities such as network

formation and/or gelly layers [5]. In normal fractionation conditions, the viscosity of crystal suspensions just

prior to filtration ranges from 300 to 2000 mPa.s depending on the application, though in palm kernel fatty

acid fractionation, viscosities over 50,000 mPa.s are not exceptional.

 Figure 3. A developing oil/crystal suspension. The darker wakes indicate spontaneous separation of the

liquid from the bulk upon stirring.

3. The Separation Stage

Although the triglyceride separation theoretically is already established during crystallization, it is clear that

the separation stage itself effectively determines the product yields as well as the stearin quality. As more

residual olein can be expelled from the solids cake, the final stearin will be more concentrated in crystals

and will turn out purer and will display higher and steeper melting. The olein quality is determined entirely

by the amount and selectivity of crystallization in the preceding stage. In some applications, the formed

crystals are often not sufficiently stress-resistant and get squeezed through the filter medium. Obviously,

such contamination of crystals in the olein phase affects the efficiency of the fractionation process negatively

and results in a liquid phase with inferior cold stable properties. Overall, the permitted degree of olein

dilution in the stearin cake determines the choice for the applied separation technology, exemplified in Table

1.
 Table 1. Different separation systems for palm oil fractionation [6].

Vacuum Centrifugal Membrane press

filtration nozzles (16 barg)

IV Palm Oil 52 52 52
IV Palm Olein 56-57 56-57 56-57
IV Palm Stearin 40-42 36 30-32
Solids in cake (%) 46 - 65
Olein Yield (%) 72 76 82

Membrane press filtration, as also used in for example sludge dewatering systems, is by far the most used

separation technology in dry fractionation nowadays. Such filters consist of a large steel frames that can

easily hold up to 150 filter plates together, each plate counting for up to 7m 2 of filtration surface and over

100L filter chamber volume (Figure 4).

Figure 4. A membrane press filter used in dry fractionation

Usually, the filter chambers are first filled with the crystal suspension, and doing so a large portion of the

liquid olein is already passing through the filter cloths. Then watertight membranes (one membrane per
chamber) attached to the internals of the plates are gradually inflated (with water, liquid oil or air) like internal

balloons to the desired pressures, reducing the chamber volume and pushing out residual liquid, which is

immediately evacuated via internal channels in the plate towards collecting tanks. The volume reduction of

the chamber thus literally compacts and dries the cake. Typical final squeeze pressures are 6 or 15barg, 30

and even 50 barg membrane press filters are available on the market to attain higher purity in speciality fat

cakes. It is also good to note that the mass fraction of solids in the filter cake decays exponentially as a

function of the distance to the filter cloth, and consequently thinner filter chambers and longer squeezing

times can be helpful (yet costly) means to reduce the entrainment significantly.

The whole filtration plus squeezing operation can vary from 30 to 90 minutes. After this, the filter plate

package is opened so the solid cakes can just drop by gravity into a stearin tank underneath the filter to

melt.

Figure 5. Hopper and stearin tank, mounted underneath the membrane press filter.

4. The Fractionation Plant Assembly

Figure 6 presents a general lay-out of a present-day dry fractionation process. Often multiple crystallizers

are used in (overlapping) series. This is not only a matter of capacity, it is also in order to maximize the use
of the filter; by a good planning of the crystallization times of filtration, the expensive (batch) filter should be

in constant operation.

Figure 6. Lay-out of a typical dry fractionation process.

The reduction of dead time of a filter can also be established by means of a crystallized offer buffer tank;

each crystallizer can be quickly drained and made ready to receive the next batch of oil, while the cooled

buffer tank will send set volumes of crystal slurry to the filter, whenever it is ready. Continuous filtration

systems have been a very elegant strategy in dry fractionation as well, although currently, the demand for

purer solid fractions as obtained by filter chamber compaction has pushed continuous belt filters somewhat

out of the dry fractionation market.

It should be kept in mind that fractional crystallization of a triglyceride oil is a relatively slow process and is

therefore the time determining stage; some simple fractionations can be established in about 5hr crystallizer

residence time, whereas more complex oils can require up to 3 days of cooling and crystal maturation before

being sent to the filter.

5. Applications and Future Developments

In essence, the goal of fractionation is to create the biggest possible difference between two fractions. Palm

oil is by far the most fractionated oil in the world. Given the broad spectrum of triglycerides and also its

naturally high amount of palmitic acid that gives a fat body at room temperature, the separation of palm oil

into sharply defined fractions usually happens in a multi-stage process (Figure 7).

Figure 7. Multistage fractionation of palm oil with possible food applications for the various the fractions

The first step of dry fractionation of palm oil yields olein fractions with a cloud point below 10C. The olein

fractions are used as a substitute for soft oils in frying, cooking and salad oils or are being further

fractionated. Together with a further development of single-stage palm oil fractionation by technological

improvements, there is an increased tendency to execute a double or triple fractionation of palm oil in order

to produce fractions with specific characteristics such as high IV superoleins (IV>65) and hard palm-mid-

fractions (hard PMF) (IV<36).

The latter fraction can serve as a feedstock for the production of typical cocoa butter equivalents (CBE),

which are non-lauric fats similar in their physical and chemical properties to cocoa butter. They are often

prepared by solvent fractionation [7], though the more contemporary developments within dry fractionation

(better suited crystallizers, improved separation technologies) are closing the gap between the quality of

solvent- and dry-fractionated hard PMF.

Another technological field of interest is the use of plug flow reactors that allow the fractional crystallization

in a continuous fashion, offering considerable reduction in operation costs (such as steam usage and

cooling power). Indeed, just as in any other edible oil processing technology, there is a continuous quest for

economization and process optimization. Heat recovery systems, crystal seeding installations, optimized

mixing procedures and elegant plant lay-outs can all contribute to maximize capacity and minimize costs for

a dry fractionation plants.

One final comment is that the process technologist should always remember that a fractionation process

yields two products, and thus that the sum of the value of the two fractions should always exceed the

processing cost and feedstock cost. This is why the feasibility of multistage fractionation is not only a matter

of technological know-how, but also a matter of having markets for all by-products generated along the way.